A process of cleaning cloth

ABSTRACT

Detergent composition for soaking or washing containing organic detergent, enzyme and hydroxylamine compound or hydrazine compound. Peroxygen compound may also be present.

iiiiiie Siaies aiei 11 1 Goheri Aug. '7, 1973 1 PROCESS OF CLEANINGCLOTH [56] References Cited [75] Inventor: Michel Rene Roger Gobert,UNITED STATES PATENTS Courbevoie, France 3,519,379 7 1970 Blomeyer e1 a1252/99 X 3,348,903 10/1967 Baler 1 1 8/111 173] Ass'gnee g g s New2,730,428 1/1956 Lindner 8/111 x or 1 2,914,374 11 1959 Harris etal..... 1. 8/111 [22] Filed: Dec. 13, 1971 3,351,655 ll/l967 Seifert 252105 x 2,077,103 4/1937 Franz 1 8/111 X [21] Appl. N0.: 207,684 2,110,6493/1938 Franz 8/111 Related US. Application Data P E w bl [63]Continuation-impart of Scr. No. 817,197, April 17, Anmary s g g em an1969, abandoned, and a continuation of Ser. No. Manley-T er en y veswr6,942, Jan. 29, 1970, abandoned.

[57] ABSTRACT 52 us. c1 8/111, 252/1310. 12, 252/89, Detergentcomposition for Soaking Orwashing Contaim I t C r bggfggg ing organicdetergent, enzyme and hydroxylamine a I 4 l I 4 l v I n in h [58] Fieldof Search 8/111; 252/1310. 12, P y e p yg pound may also be present.

12 Claims, N0 Drawings PROCESS OF CLEANING CLOTH This application is acontinuation-in-part of my copending application, Ser. No. 817,197,filed Apr. 17, 1969, now abandoned, and a continuation of Ser. No.6,942, filed Jan. 29, 1970, now abandoned.

This invention relates to detergent compositions including an enzyme andan agent for improving the detergent effect.

Enzymes have been incorporated into detergent compositions since theyare particularly effective against various common stains which are fixedto textiles and laundry. In particular, proteolytic enzymes, whichpossess the ability to digest and degrade protein matter, are effectivein removing from textiles and laundry proteinic stains such as blood,sweat, milk, cocoa, gravy and other sauces and the like. This digestionor degradation of protein matter facilitates removal of dirt by thedetergent.

in accordance with one aspect of this invention, a hydroxylaminecompound or hydrazine compound is added to the enzyme-containingdetergent composition. It is found that the presence of thehydroxylamine compound or hydrazine compound increases the effectivenessof the enzyme-containing detergent composition, both during the soakingstep and the washing step.

The hydroxylamine compound or hydrazine compound may be employed invarying amounts. One suitable range is about 1 to percent of thedetergent composition.

The surface active agent which may be employed may be any commonly usedcompound having surface active or detergent properties. Most preferredare those water-soluble surface active compounds having anionic ornonionic properties. Anionic surfaces active agents include thosesurface active or detergent compounds which contain an organichydrophobic group and an anionic solubilizing group. Typical examples ofanionic solubilizing groups are sulfonate, sulfate, carboxylate andphosphate. Examples of suitable anionic detergents which fall within thescope of the invention include the soaps, such as the water-solublesalts of higher fatty acids or rosin acids, such as may be derived fromfats, oils and waxes of animal, vegetable or marine origin, e.g., thesodium soaps of tallow, grease, coconut oil, tall oil and mixturesthereof; and the sulfated and sulfonated synthetic detergents,particularly those having about 8 to 26, and preferably about 12 to 22,carbon atoms to the molecule.

As examples of suitable synthetic anionic detergents there may be citedthe higher alkyl mononuclear aromatic sulfonates such as the higheralkyl benzene sulfonates containing from 10 to 16 carbon atoms in thealkyl group in a straight or branched chain, e.g., the sodium salts ofdecyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, orhexadecyl benzene sulfonate and the higher alkyl toluene, xylene andphenol sulfonates; alkyl naphthalene sulfonate, ammonium diamylnaphthalene sulfonate, and sodium dinonyl naphthalene sulfonate;sulfated aliphatic alcohols such as sodium lauryl and hexadecylsulfates, triethanolamine lauryl sulfate, and sodium oleyl sulfate;sulfated alcohol ethers, such as lauryl, tridecyl, or tetradecylsulfates including 2-4 ethylene oxide moieties; sulfated and sulfonatedfatty oils, acids or esters, such as the sodium salts of sulfonatedcaster oil and sulfated red oil; sulfated hydroxyamides such as sulfatedhydroxy-ethyl lauramide; sodium salt of lauryl sulfoacetate; sodium saltof dioctyl sulfosuccinate; and the sodium salt of oleyl methyl tauride.

Other anionic surface active agents which may be employed in thepractice of this invention include ole fin sulfonates, typicallycontaining eight to 25 carbon atoms.

Also included within the ambit. of the invention are the sulfuric acidesters of polyhydric alcohols incompletely esterified with higher fattyacids, e.g., coconut oil monoglyceride monosulfate, tallow diglyceridemonosulfate; and the hydroxy sulfonated higher fatty acid esters such asthe higher fatty acid esters of low molecular weight alkylol sulfonicacids, e.g. oleic acid ester of isethionic acid.

Nonionic surface active agents are those surface active or detergentcompounds which contain an organic hydrophobic group and a hydrophilicgroup which is a reaction product of a solubilizing group such ascarboxylate, hydroxy], amido or amino with ethylene oxide or with thepolyhydration product thereof, polyethylene glycol.

As examples of nonionie surface active agents there may be noted thecondensation products of alkyl phenols with ethylene oxide, e.g., thereaction product of isooctyl phenol with about six to 30 ethylene oxideunits; condensation products of alkyl thiophenols with 10 to 15 ethyleneoxide units; condensation products of higher fatty alcohols such astridecyl alcohol with ethylene oxide; ethylene oxide addends ofmonoesters of hexahydric alcohols and innerethers thereof such assorbitan monolaurate, sorbitol mono-oleate and mannitan monopalmitateand the condensation products of polypropylene glycol with ethyleneoxide.

Cationic surface active agents may also be employed. Such agents arethose surface active detergent compounds which contain an organichydrophobic group and a cationic solubilizing group. Typical cationicsolubilizing groups are amine and quaternary groups.

As examples of suitable synthetic cationic detergents there may be notedthe diamine such as those of the type RNHC H NH wherein R is an alkylgroup of about 12 to 22 carbon atoms, such as N-aminoethyl stearyl amineand N-amino-etlhyl myristyl amine; amide-linked amines such as those ofthe type RCONHC TLNIH wherein R is an alkyl group of about 12 to 18carbon atoms, such as N-amino ethylstearyl amide and N-amino ethylmyristyl amide; quaternary ammonium compounds wherein typically one ofthe groups linked to the nitrogen atom is an alkyl group of about 12 to18 carbon atoms and three of the groups linked to the nitrogen atom arealkyl groups which contain one to three carbon atoms, including such oneto three carbon alkyl groups bearing inert substituents, such as phenylgroups, and there is present an anion such as halogen acetate,methosulfate, etc. Typical quaternary ammonium detergents areethyldimethyl-stearyl ammonium chloride, benzyl-dimethylstearyl ammoniumchloride, trimethyl stearyl ammonium chloride, trimethylcetyl ammoniumbromide, methyl-ethyl-di-lauryl ammonium chloride,dimethylpropyl-myristyl ammonium chloride, and the correspondingmethosulfates and acetates.

The surface active compounds which are used in the most preferredaspects of this invention are those having anionic properties. The mosthighly preferred water soluble anionic detergent compounds are theammonium and substituted ammonium (such as mono-, di-

and triethanolamine), alkali metal (such as sodium and potassium) andalkaline earth metal (such as calcium and magnesium) salts of the higheralkyl benzene sulfonates, the higher alkyl sulfates, and the higherfatty acid monoglyceride sulfates. The particular salt will be suitablyselected depending upon formulation and the proportions therein.

The surface active agent is typically present in amount of about -95percent by weight of the detergent composition, preferably -25 percentby weight.

The proteolytic enzymes which are employed in the instant invention areactive upon protein matter and catalyze digestion or degradation of suchmatter when present as in linen or fabric stain in a hydrolysisreaction. The enzymes are effective at a pH range of about four to 12,such as usually prevails in detergent cleaning procedures. Moreover,they may be effective even at moderately high temperatures so long asthe temperature does not degrade them. Some proteolytic enzymes areeffective at up to about 80C. and higher. They are also effective atambient temperature and lower to about 10C. Particular examples ofproteolytic enzymes which may be used in the instant invention includepepsin, trypsin, chymotrypsin, papain, bromelin, colleginase,keratinase, carboxylase, amino peptidase, elastase, subtilisin andaspergillopepidase A and B. Preferred enzymes are subtilisin enzymesmanufactured and cultivated from special strains of spore formingbacteria, particularly Bacillus subtilis.

Metalloproteases which contain divalent ions such as calcium, magnesiumor zinc bound to their protein chains are of interest.

The enzyme preparations are generally extremely fine, oftensubstantially impalpable, powders. In a typical powdered enzymepreparation the particle diameter is mainly below 0.15 mm. generallyabove 0.01 mm, e.g. about 0.1 mm; for example, as much as 75 percent ofthe material may be 0.149 mm or smaller. On the other hand the spraydried granules are usually of very much larger particle size, with themajor portion of the granules being at least about 0.2 mm in diameter,e.g. about 0.3 or 0.4, or even 0.5, 1 or 2 mm.

The enzyme preparations are generally diluted with salts such as calciumsulfate and inert materials. Chemically they are typically stable in thepH of 5 to 10 and at an alkaline pH of 8.5 to 9 they can withstandtemperatures of 49C to 77C. with relatively little decomposition fortime periods varying from 2 hours at the higher temperatures to morethan 1 day at the lower temperatures. Different proteolytic enzymes havediffernet degrees of effectiveness in aiding in the removal of stainsfrom textiles and linen.

The enzyme is preferably present in powdered form and is admixed intothe detergent formulation. It is typically present in amount of about0.001 percent 4 percent by weight of the detergent composition,preferably about 0.05 1 percent, e.g., about 0.1 0.5 percent.

In addition to the materials described above, the detergent compositionof the invention may be any of the water-soluble inorganic builder saltscommonly known in the art, or it may be a water-soluble organicsequestering agent such as sodium nitrilotriacetate, or mixturesthereof.

The water-soluble inorganic builder salts may be suitable alkali metal,alkaline earth metal, or heavy metal salt or combinations thereof.Ammonium or an ethanolammonium salt in a suitable amount may be addedalso, but generally the sodium and potassium salts are preferred.Examples are the water-soluble sodium and potassium phosphates,silicates, carbonates, bicarbonates, borates, sulfates and chlorides.Particularly preferred builder salts are the alkaline builder salts suchas polyphosphates, silicates, borates, etc.

In the water-soluble inorganic builder salt mixtures used in thedetergent compositions, it is often preferred to have present a mixtureof sodium tripolyphosphate and sodium or potassium bicarbonate, such asa combination or mixture of salts wherein the bicarbonate totripolyphosphate ratio is selected from the range of about 1:1 to about3:1.

Both Phase I and Phase 11 sodium tripolyphosphate and mixtures thereofmay be successfully used in the compositions. The usual commercialtripolyphosphate consists mainly of the Phase 11 material. Thecommercial tripolyphosphate material is usually essentiallytripolyphosphate, e.g. 87-95 percent, with small amounts, e.g. 4-13percent of other phosphates, e.g. pyrophosphate and orthophosphate.Sodium tripolyphosphate in its hydrated form may be used also. Trisodiumorthophosphate may be used in the amounts indicated.

The sodium or potassium bicarbonate is an effective pH buffer. Thebicarbonate may be incorporated directly as anhydrous bicarbonate or inthe form of sesquicarbonate, a hydrate containing both bicarbonate andcarbonate.

Other suitable builder salts which may be present include thewater-soluble sodium and potassium silicates, carbonates, borates,chlorides and sulfates.

Generally, when present, the builder salt is employed in amount of about50-90 percent by weight of the detergent composition.

The detergent composition may also contain additives such as sodiumcarboxymethylcellulose or polyvinyl-pyrollidone. These additives may bepresent in amount of about 0.1 percent 5 percent by weight of thedetergent composition. The detergent composition may also include minoramounts of optical brighteners, perfumes and preservatives. A peroxygencompound may also be present, such as sodium perborate in amount of, forinstance, about 3 to 35 percent of the detergent composition. Whenperoxygen compound is present, it is best to use larger amounts of thehydroxylamine compound or hydrazine compound.

The hydroxylamine compound or hydrazine compound may be added as such orin the salt form, e.g. as the hydrochlorides, sulfates, nitrates,phosphates, flurosilicates, formates, or oxalates. Hydroxylamine,hydrazine, phenyl hydrazine, carbamoyl hydrazine, N-phenyl-N'-carbamoyl-hydrazine are examples of suitable compounds. Whensubstituted hydroxylamine or hydrazine compounds are employed, theyshould retain at least one unsubstituted hydrogen on the hydroxylamineor hydrazine nucleus; thus, mono, dior trisubstituted hydrazine may beused. The substituent, or substituents, may be alkyl, e.g. methyl orbutyl, or aryl, e.g. phenyl, or of other types, e.g. carbamyl.

The following Examples are given to illustrate this invention further.All proportions therein, and elsewhere in this application, are byweight unless otherwise indicated.

EXAMPLE 1 This Example shows the effect of addition of hydroxylaminehydrochloride to an enzyme-containing detergent composition, for boththe soaking step and the washing step.

A. The soaking solution is a solution, in water, of (a) a commercialbuilt synthetic detergent composition (described in detail below) inconcentration of 5 grams per liter, (b) a commercially availableproteolytic enzyme composition (Alcalase) in concentration of 0.05 gramsper liter, and (c) sodium perborate in concentration of 0.005 M. Whereindicated, hydroxylamine hydrochloride is also present. Standard testsamples of soiled cotton fabrics carrying substantial colored stain ofprotein nature (such as blood, sweat, milk, cocoa, gravy and the like,carrying carbon black pigment) are soaked in the soaking solution atroom temperature for 60 minutes; grams of soiled fabric are present perliter of soaking solution.

After the 60 minute soaking, the fabrics are removed from the solution(and then rinsed). The reflectance of the fabrics is then measured. Anincrease in reflectance indicates, of course, an improvement in thecleanliness of the samples.

The following tabulation shows the improvement obtained by thehydroxylamine hydrochloride:

concentration of NH oH-HCl (in mols per liter) 0 0.0001 0.0004 0.001reflectance l8 19 20 21 concentration of NH OH-HCI mols per liter) 0reflectance 23 EXAMPLE 2 in this Example, an enzyme-containing soakingsolution identical with that of Example 1A is employed, except that noperborate is present. The soaking conditions are the same as those ofExample 1A.

The following tabulation shows the improvement in reflectance obtainedby the inclusion of various amounts of hydroxylamine hydrochloride inthe solu-' tron:

concentration of NH OH'HCI (in mols per liter) 0 reflectance 39 EXAMPLE3 Example 1 is repeated using hydrazine sulfate in place of thehydroxylamine hydrochloride. The following results are obtained:

Concentration of Hydrazine sulfate Reflectance after Reflectance after(in mols per liter) soaking step washing step 0 2l 24 0.0001 21 260.0002 2! 26 0.0004 22 26 0.0006 22 Ill 0.0008 23 30 0.001 22 29 0.00221 29 0.004 25 36 0.006 24 34 The commercial detergent composition usedin Examples 1-4 has the following composition:

sodium dodecyl benzene sulfonate 17 sodium tripolyphosphate 26 sodiumsilicate (1:2 sio,= Na,0 mol ratio) 6 sodium carboxymethylcellulose 0.optical brightener 0 perfume 0 preservative moisture sodium sulfate Theproteolytic enzyme Alcalase used in Examples l4 is characterized ashaving its maximum proteolytic activity at a pH of 8-9. This activity ismeasured on the commercial enzyme available from Novo lndustri A/S,Copenhagen, Denmark is about 1.5 Anson Units per gram of the enzyme. Thecommercial enzyme is a raw extract of bacillus subtillis culture andcontains about 6 percent of pure crystallized proteolytic material.

EXAMPLE 4 In this Example soiled fabric carrying proteinic stain issoaked for 60 minutes at room temperature in a solution containing 0.05percent Alcalase, 0.0062 mol per liter of sodium perborate and 5 g literof the commercial detergent composition in water together with 0.002 molper liter of one of the compounds listed in the table below. The soakedfabric is then washed (with periodic agitation) in a fresh solution ofthe same composition as the soaking solution for 30 minutes at -l0OC.

The results are expressed in the turbidity of (a) the used soakingsolution, (b) the turbidity of the used washing solution and (ab) thesum of these two'turbidities. An increase in turbidity of the solutionhas been found to indicate that more of the soil has been transferredfrom the fabric to the solution during use.

In making the turbidity tests the proteins in the liquid are firstprecipitated by addition of sulfonic acid and the optical density of theresulting dispersion of proteins is measured using light whosewavelength is 405 m.

Two types of soiled fabrics are used: one is soiled with chocolate andthe other (designated in the table below as (biosoil") is the same asthat used in Example l.

Additive Stain Turbidity a I) ah none (control) chocolate 9 ll 20 phenylhydrazine 1723 40 hydrochloride hydrazine sulfate 9 19 28N-phenyl-N-carbamylhydrazine hydroxylamine sulfate 1214 26 none(control) biosoil 2320 43 phenyl hydrazine hydrochloride 3326 59hydroxylamine sulfate 3223 55 hydrazine sulfate 2728 55 hydrazine 3124 55 N-carbamylhydrazine hydrochloride 2324 47 As is well known, sodiumperborate is available commercially in two forms, the monohydrate andthe tetrahydrate. This invention is useful with both these forms. In theforegoing Examples the tetrahydrate form of the sodium perborate isused. Excellent results are also obtained when the monohydrate form isemployed.

It is understood that many variations may be made herein withoutdeparting from the spirit of the inven- U011.

I claim:

1. A process of cleaning cloth comprising treating said cloth with watercontaining a detergent composition consisting essentially of an organicwater-soluble detergent and a proteolytic enzyme effective at a pH rangeof about four to 12 and a compound selected from the group consisting ofa hydroxylamine compound and a hydrazine compound, each compound havingat least one unsubstituted hydrogen on the hydroxylamine or hydrazinenucleus of said compound, said detergent being selected from the groupconsisting of anionic, nonionic and cationic detergents, saidcomposition containing about to 95 percent by weight of said detergent,about 0.001 to 4 percent by weight of said enzyme and about 1 to percentby weight of said compound.

2. A process of cleaning cloth as in claim 1 in which the organicdetergent is an anionic surface active agent.

3. A process of cleaning cloth as in claim 1 in which about 50 to 90percent by weight of a water-soluble inorganic builder salt is alsopresent.

4. A process of cleaning cloth as in claim 1 in which about 50 topercent by weight of an organic sequestering agent is also present.

5; A process of cleaning cloth as in claim 1 in which said compound is ahydrazine compound.

6. A process of cleaning cloth .as in claim 1 in which said compound isa hydroxylamine compound.

7. A process of cleaning cloth as in claim 1 in which said compound isphenyl hydrazine. v

8. A process of cleaning cloth as in claim 1 in which said compound isN- phenyl-N-carbamyl hydrazine.

9. A process of cleaning cloth as in claim 1 wherein said cloth issoaked in water containing said composition and then washed in watercontaining said composition.

10. A process of cleaning cloth as in claim 1 in which sodium perbo rateis also present in said composition in amount of about 3 to 35 percentby weight.

1 l. A process of cleaning cloth as in claim 6 in which said compound ishydroxylamine sulfate.

12. A process of cleaning cloth as in claim 9 wherein said cloth issoaked in'water containing said composition and then washed in watercontaining said composition.

2. A process of cleaning cloth as in claim 1 in which the organicdetergent is an anionic surface active agent.
 3. A process of cleaningcloth as in claim 1 in which about 50 to 90 percent by weight of awater-soluble inorganic builder salt is also present.
 4. A process ofcleaning cloth as in claim 1 in which about 50 to 90 percent by weightof an organic sequestering agent is also present.
 5. A process ofcleaning cloth as in claim 1 in which said compound is a hydrazinecompound.
 6. A process of cleaning cloth as in claim 1 in which saidcompound is a hydroxylamine compound.
 7. A process of cleaning cloth asin claim 1 in which said compound is phenyl hydrazine.
 8. A process ofcleaning cloth as in claim 1 in which said compound isN-phenyl-N''-carbamyl hydrazine.
 9. A process of cleaning cloth as inclaim 1 wherein said cloth is soaked in water containing saidcomposition and then washed in water containing said composition.
 10. Aprocess of cleaning cloth as in claim 1 in which sodium perborate isalso present in said composition in amount of about 3 to 35 percent byweight.
 11. A process of cleaning cloth as in claim 6 in which saidcompound is hydroxylamine sulfate.
 12. A process of cleaning cloth as inclaim 9 wherein said cloth is soaked in water containing saidcomposition and then washed in water containing said composition.